OPEN , magnetic, and electronic

SUBJECT AREAS: structures, and properties of new MAGNETIC PROPERTIES AND MATERIALS BaMnPnF(Pn 5 As, Sb, Bi) SUPERCONDUCTING PROPERTIES AND MATERIALS Bayrammurad Saparov1, David J. Singh1, Vasile O. Garlea2 & Athena S. Sefat1 -STATE

ELECTRONIC PROPERTIES AND 1Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA, 2Quantum Condensed MATERIALS Matter Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA.

Received New BaMnPnF(Pn 5 As, Sb, Bi) are synthesized by stoichiometric reaction of elements with BaF2. They 26 March 2013 crystallize in the P4/nmm space group, with the ZrCuSiAs-type structure, as indicated by X-ray crystallography. Electrical resistivity results indicate that Pn 5 As, Sb, and Bi are semiconductors with band Accepted gaps of 0.73 eV, 0.48 eV and 0.003 eV (extrinsic value), respectively. Powder neutron diffraction reveals a 20 June 2013 G-type antiferromagnetic order below TN 5 338(1) K for Pn 5 As, and below TN 5 272(1) K for Pn 5 Sb. Magnetic susceptibility increases with temperature above 100 K for all the materials. Density functional Published calculations find semiconducting antiferromagnetic compounds with strong in-plane and weaker 8 July 2013 out-of-plane exchange coupling that may result in non-Curie Weiss behavior above TN. The ordered magnetic moments are 3.65(5) mB/Mn for Pn 5 As, and 3.66(3) mB/Mn for Pn 5 Sb at 4 K, as refined from neutron diffraction experiments. Correspondence and requests for materials he recent discovery of high temperature superconductivity in F-doped LaFeAsO1 (1111 family) initiated an should be addressed to extensive research into analogous materials. This research led to the discoveries of superconductivity in B.S. (saparovbi@ornl. 2,3 4 5 T doped BaFe2As2 (122 family), LiFeAs (111 family), and FeSe (11 family), among others. All these families gov) feature two dimensional (2D) structures with FeAs or FeSe layers, which contain edge-shared FeAs4 or FeSe4 tetrahedra. Fe are formally divalent; hole-, electron-, or isovalent-doping inside or outside of layers can result in superconductivity. Among the Fe-based superconductors (FeSCs), the highest superconducting transition temperatures (TCs) are reported for the 1111 family6,7. In the search for non-Fe-based , varieties of physical properties are found such as diamagnetism in LaZnAsO8, itinerant ferromagnetism in LaCoAsO9,10, semiconducting antiferro- 11 12 magnetism in LnMnPnO (Ln 5 La-Sm; Pn 5 P, As) and superconductivity in LaNiAsO (TC , 3 K). Interestingly, although such have been studied in detail, reports on non- 1111 fluoroarsenides with ZrCuSiAs-type structure, i.e. BFeAsF (B 5 alkaline- ), are relatively scarce. For the 1111 fluopnictides BFeAsF, rare-earth substitution at the alkaline-earth metal (B) site is found to give the 13,14 highest TC of 56 K for Sr0.5Sm0.5FeAsF and Ca0.4Nd0.6FeAsF . The only known non-Fe transition-metal-based 1111 fluoropnictides are BaMnPF15, ACuChFandAAgChF(A 5 Sr, Ba, Eu; Ch 5 S, Se, Te)16,17.However,itshould be noted that Cu and Ag in ACuChFandAAgChF are nominally monovalent, and therefore, BaMnPF is the only known 1111 fluoropnictide containing divalent non-Fe . Other known 1111 fluoropnictides, include those of group 12 , namely SrZnPF, BaZnPF, BaZnSbF and BaCdSbF15,18. According to literature on the properties of 1111 fluoropnictides, SrCuChF19,20,BaCuChF21 and EuCuChF20 (Ch 5 S, Se and Te) are p-type semiconductors with Seebeck coefficients ranging from 110 to 1620 mV/K. BaZnPF15 and BaCdSbF18 are also semiconductors with band gaps of Eg 5 0.5 eV and 0.25 eV, respectively. Moreover, BaMnPF is a semiconducting antiferromagnet with a temperature independent magnetic susceptibility up to 300 K15. Considering the fact that doped BFeAsF fluoropnictides are among the highest TC (56 K) FeSCs, there is an incentive to explore for superconductivity in similar 1111 structures, and even non-Fe-based analogs. This is the report of the synthesis of new 1111 ZrCuSiAs-type BaMnPnF(Pn 5 As, Sb, Bi) (Figure 1) and a comprehensive study of their crystal, magnetic, and electronic structures. We report nuclear structures from powder and single crystal X-ray diffraction, and magnetic structures from neutron powder diffraction. In addition, we present thermodynamic and transport properties from temperature dependent electrical transport data, temperature- and field-dependent magnetization data. Moreover, we report density functional theory (DFT) electronic struc- ture calculations.

SCIENTIFIC REPORTS | 3 : 2154 | DOI: 10.1038/srep02154 1 www.nature.com/scientificreports

Table 2 | For BaMnPnF(Pn 5 Sb, Bi), atomic coordinates and a equivalent isotropic (Ueq ) displacement parameters, at 173 K, from single crystal X-ray diffraction refinements

˚ 2 Wyckoff site xy zUeq (A ) BaMnSbF Ba 2c 0.25 0.25 0.3539(1) 0.0113(3) Mn 2a 0.25 0.75 0 0.0117(4) Sb 2c 0.25 0.25 0.8321(1) 0.0108(3) F2b 0.25 0.75 0.5 0.013(1) BaMnBiF Ba 2c 0.25 0.25 0.3585(2) 0.0205(5) Mn 2a 0.25 0.75 0 0.0210(8) Bi 2c 0.25 0.25 0.8245(1) 0.0205(4) F2b 0.25 0.75 0.5 0.023(3)

Figure 1 | Tetragonal ZrCuSiAs-type structure of BaMnPnF(Pn 5 As, a Ueq is defined as one third of the trace of the orthogonalized Uij tensor. Sb, Bi). The unit cell contains transition metal pnictide layers of 2 [MnPn] that are made of MnPn4 tetrahedra. distances shown by the distance between and Results atoms in adjacent layers are dBa-Sb 5 3.6489(6) A˚ in BaMnSbF and ˚ Synthesis, crystal chemistry, and stability. Three new compounds dBa-Bi 5 3.671(1) A in BaMnBiF. For comparison, MnAs4 tetrahedra of BaMnAsF, BaMnSbF and BaMnBiF are synthesized using the in BaMnAsF are characterized by the distances dMn-As 5 2.60460(4) ˚ ˚ solid-state method. The compounds crystallize in the A and dMn-Mn 5 3.0221(1) A, and bond angles 109.0789(8)u and primitive ZrCuSiAs-type tetragonal P4/nmm (No. 139, Pearson 110.259(2)u, from the room temperature PXRD data (see Table symbol tP8), and are isotypic to the lighter BaMnPF (Figure 1)15. S1). The bond distances and angles in BaMnPnF are very close to 24–26 EDS results confirm the presence of small crystallites with those reported for the related BaMn2Pn2 ternary phases , which 2 2 BaMnSbF and BaMnBiF compositions after the first heating step, also contain anionic ? [MnPn] layers. which allows for collection of single-crystal x-ray diffraction data PXRD patterns along with Rietveld refinements results for (Table 1). There are four crystallographically unique atoms in the BaMnAsF, BaMnSbF and BaMnBiF are illustrated in Figures 2 to 4. asymmetric unit cell, all located in special positions (Tables 2, 4, S1). There are no Bragg peaks in the 2h range of 5–20u for Pn 5 As and BaMnPnF structure, similar to LaFeAsO, can be viewed with cationic Sb, and so the low angle regions are not shown for them. The broad 2 1 2 2 ?[BaF] and anionic ? [MnPn] layers alternating along the c-axis. background below 2h , 25u in Pn 5 Sb and Bi (Figure 3–4) are These layers are built upon edge-sharing FBa4 and MnPn4 tet- caused by the polycarbonate cover. X-ray diffraction refinement rahedra, respectively. Following the discovery of superconductivity detects a small amount of BaF2 crystalline (less than 1% in the F-doped LaFeAsO, the ZrCuSiAs-type structure and its rela- by mass) in Pn 5 As and Bi products, whereas no impurity peaks are tionship with other structures have been extensively studied11,22,23. observed in the Pn 5 Sb compound. From single crystal X-ray data (Table 3), Mn-Sb and Mn-Bi bond All BaMnPnF samples have MnO if ground in air dur- 2 ˚ distances in the [MnPn] layers are dMn-Sb 5 2.7767(5) A and dMn-Bi ing sample sintering stages. Even in the final product form, ground- ˚ 5 2.8479(11) A, respectively; the Mn-Mn distances are dMn-Mn 5 in-air BaMnSbF shows signs of oxidation in the PXRD data, while ˚ ˚ 3.1595(4) A in BaMnSbF and dMn-Mn 5 3.196(1) A in BaMnBiF. The BaMnBiF burns in air. The extreme air sensitivity of ground tetrahedral angles are 110.65(1)u and 107.14(3)u in MnSb4, and BaMnBiF limits its full characterization through neutron diffraction 111.73(3)u and 105.04(5)u in MnBi4 tetrahedra. The interlayer experiments. Notwithstanding these facts, the heating of pellets under ambient conditions up to 130uC and subsequent PXRD mea- surements demonstrate that BaMnPnF are air-stable in pellet form. 5 Table 1 | For BaMnPnF(Pn Sb, Bi), selected single crystal X-ray The refined room temperature lattice parameters from the PXRD diffraction data and structure refinement parameters data are a 5 4.2739(1) A˚ and c 5 9.5875(2) A˚ for BaMnAsF (Rp 5 Empirical formula BaMnSbF BaMnBiF 8.54%, wRp 5 11.52%), a 5 4.4791(1) A˚ and c 5 9.8297(2) A˚ for BaMnSbF (Rp 5 4.59%, wRp 5 6.03%), and a 5 4.5384(1) A˚ and c 5 Temperature, K 173(2) 9.8929(2) A˚ for BaMnBiF (Rp 5 4.05%, wRp 5 5.40%). The refine- Radiation, A˚ Mo Ka, 0.71073 Crystal system Tetragonal ment of PXRD data on BaMnAsF and BaMnSbF show (Figures 2b, Space group, ZP4/nmm (No. 129), 2 Formula weight, g mol21 333.03 420.26 ˚ a,A˚ 4.4682(6) 4.5198(14) Table 3 | For BaMnPnF(Pn 5 Sb, Bi), selected bond distances (A) c,A˚ 9.817(3) 9.875(7) and angles (u), at 173 K, from single crystal X-ray diffraction V,A˚ 3 196.00(6) 201.74(16) 23 BaMnSbF BaMnBiF rcalc,gcm 5.643 6.918 m 21 ,mm 19.736 56.034 F–Ba (34) 2.6549(5) F–Ba (34) 2.6572(12) hmin 2 hmax, u 2.07–28.20 2.06–28.50 3 3 a Mn–Sb ( 4) 2.7767(5) Mn–Bi ( 4) 2.8479(11) R1 (all data) 0.0248 0.0388 a Mn–Mn 3.1595(4) Mn–Mn 3.1960(10) wR2 (all data) 0.0644 0.0963 2 Ba–Sb 3.6489(6) Ba–Bi 3.6714(14) Goodness-of-fit on F 1.23 1.11 Sb–Mn–Sb 110.65(1) Bi–Mn–Bi 111.73(3) 2 ˚ 23 2 2 Largest peak and hole, e A 3.35 and 0.95 3.18 and 1.79 Sb–Mn–Sb 107.14(3) Bi–Mn–Bi 105.04(5) P P P P a ~ { ~ 2{ 2 2 2 21=2 ~ 2 2z 2z R1 jjjjFo jjFc = jjFo ; wR2 w(Fo Fc ) = w(Fo ) and w 1= s Fo (AP) BP , Ba–F–Ba 114.60(3) Ba–F–Ba 116.53(7) ~ 2z 2 and P (Fo 2Fc )=3; A and B are weight coefficients. Ba–F–Ba 106.97(1) Ba–F–Ba 106.06(3)

SCIENTIFIC REPORTS | 3 : 2154 | DOI: 10.1038/srep02154 2 www.nature.com/scientificreports

visual change occurs to the pellets up to ,1430 K, after which molten Table 4 | Refined structural parameters for BaMnAsF and BaMnSbF liquid is clearly visible in both samples. These molten pieces contain at 4 K from neutron powder diffraction, in P4/nmm MnAs and MnSb binaries according to the EDS results. Atom Wyckoff site xy z B(A˚ 2) Physical properties. For BaMnPnF, temperature dependence of BaMnAsF ˚ ˚ electrical resistivity results are plotted in Figure 5. The compounds a 5 4.2642(1) A, c 5 9.5586(3) A show semiconducting behavior, with room temperature resistivity 5 Ba 2c 0.25 0.25 0.3386(5) 0.09(8) values of r300K(BaMnAsF) 5 3.6 3 10 V cm, r300K(BaMnSbF) 5 2.4 4 Mn 2a 0.25 0.75 0 0.12(7) 3 10 V cm, and r300K(BaMnBiF) 5 0.135 V cm. Similarly, BaMnPF As 2c 0.25 0.25 0.8459(3) 0.12(6) is also reported as a semiconductor15. The semiconducting behavior F2b 0.25 0.75 0.5 0.29(6) supports the charge-balanced nature of the compounds according to 21 2 21 32 BaMnSbF [Ba F ][Mn Pn ]. dr/dT derivatives of the resistivity data are a 5 4.4636(1) A˚ , c 5 9.7885(4) A˚ featureless in the measured range. Calculated band gaps from the Arrhenius fit (lnr 5 lnr0 1 Eg/2kBT) are Eg(BaMnAsF) 5 0.73 eV, Ba 2c 0.25 0.25 0.3546(4) 0.05(7) Eg(BaMnSbF) 5 0.48 eV, and Eg(BaMnBiF) 5 0.003 eV (see Mn 2a 0.25 0.75 0 0.29(8) Figure 5). These band gap values follow the expected periodic Sb 2c 0.25 0.25 0.8316(4) 0.15(7) trend based on of pnictogen elements28.Itis F2b 0.25 0.75 0.5 0.48(6) interesting that for BaMnBiF, both the temperature dependence of electrical resistivity and the calculated narrow band gap are quite 3b) that there are no structural anomalies upon cooling and the unit different when compared to the other Pn members. For BaMnBiF, cell volumes contract uniformly. A survey of the Inorganic Crystal r(T) decreases upon cooling down to ,85 K, then changes slope and Structure Database (ICSD)16 and the Pearson’s Handbook17 reveals sharply increases below 80 K. From the trend in the band gaps in new features about the BaMnPnF family. First, they are the only this family, it can be speculated that BaMnBiF is an extrinsic reported compounds in each of the corresponding Ba-Mn-Pn-F semiconductor29. (Pn 5 As, Sb, Bi) phase diagrams so far. Second, BaMnBiF can also The calculated band gaps for BaMnAsF and BaMnSbF are two be considered to be the first bismuthide with the ZrCuSiAs-type orders of magnitude larger than those reported for the narrow gap 27 24–26 structure, considering that Bi in BiCuSeO serves as a cation. semiconductors of BaMn2Pn2, with band gaps of 6–54 meV . Third, together with BaMnPF, the new compounds are the first Such a difference may be attributed to the fact that BaMnPnF contain phases with Mn and F to adopt the ZrCuSiAs structure type. an additional insulating [BaF]1 layer in the structure, which reduces Fourth, the cell volumes of BaMnSbF and BaMnBiF (see Table 1) the band dispersion in the c-axis direction. Further comparisons can are the largest within this structure type along with that of be made with the isostructural quaternary phases based on mangan- BaCdSbF18. As expected from the large unit cell volumes and lattice ese. Most of LnMnPnO(Ln 5 rare-earth metal) compositions have parameters of BaMnSbF and BaMnBiF, the bond distances are also been reported to be semiconductors with varying band gaps11, with longer than those reported for other compounds that adopt this exceptions such as metallic PrMnSbO30. structure type8,11. Temperature- and field-dependent magnetization results for The thermal behaviors of BaMnAsF and BaMnSbF are studied BaMnAsF are plotted in Figure 6a. ZFC and FC x(T) data overlap through TGA/DTA (Figure S1). Both BaMnAsF and BaMnSbF are for BaMnAsF, and are measured up to ,800 K. There is an upward stable up to 1300 K (,1030uC), after which they decompose. tail in x(T)below,15 K, which is probably due to paramagnetic Additionally, pellets of BaMnAsF and BaMnSbF are separately impurities, above which magnetic susceptibility increases slowly with vacuum sealed inside silica tubes and heated to 1500 K with periodic rising temperature. There is another change in the slope of x(T)at visual monitoring. This is done because the DTA on BaMnAsF ,550 K, above which x(T) starts to plateau. M(H) plots both at 5 K (Figure S1) shows two peaks upon heating, and it is not immediately and 100 K are linear. x(T)andM(H) data, coupled with resistivity clear if the first peak corresponds to the melting of the compound. No data, suggest that BaMnAsF is likely a local moment antiferromagnet.

Figure 2 | For BaMnAsF, (a) Rietveld refinement (red line) of powder X-ray diffraction data (black dots), shown along with Bragg positions for 1111 tetragonal I4/mmm phase (pink tick marks) and BaF2 impurity (turquoise tick marks); (b) temperature-dependence of refined lattice parameters (dash lines are guide to the eye).

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Figure 3 | For BaMnSbF, (a) Rietveld refinement (red line) of powder X-ray diffraction data (black dots), shown along with Bragg positions for 1111 tetragonal I4/mmm phase (pink tick marks) with no impurities; (b) temperature-dependence of refined lattice parameters (dash lines are guide to the eye). The green data points in (b) are a- and c- lattice parameters from single crystal X-ray diffraction refinements.

Field dependence of magnetization (not shown) for BaMnSbF and Neutron powder diffraction. Results of the neutron powder diffrac- BaMnBiF suggest presence of ferromagnetic impurities. From a lin- tion (NPD) experiments are summarized in Table 4, and Figures 7 ear fit to the M(H) data at 5 K, saturation magnetization values of and 8, and S2 to S4. Rietveld refinement of the NPD data at 4 K gives Msat(BaMnSbF) 5 0.039 mB/mol Mn, and Msat(BaMnBiF) 5 lattice parameters of a 5 4.2642(1) A˚ and c 5 9.5586(3) A˚ for 0.006 mB/mol Mn are obtained. Assuming that the sources of the BaMnAsF (RBragg 5 3.54%, RF 5 2.4%), and a 5 4.4636(1) A˚ and 16,17 ferromagnetic impurities are MnSb or MnBi binaries , the Msat c 5 9.7885(4) A˚ for BaMnSbF (RBragg 5 4.85%, RF 5 3.2%). Magnetic values correspond to 1.2% (molar) MnSb, or 0.13% MnBi impurity peaks can be indexed by a wave vector k 5 (0 0 1/2), giving a concentrations. Consequently, in order to find intrinsic behavior for magnetic structure (Figure 8a) with antiferromagnetic (AF) BaMnSbF and BaMnBiF compounds, magnetic susceptibility mea- coupling between nearest-neighbor Mn in the [MnPn]2 surements were performed under two applied fields (20 kOe and 30 layers. The adjacent [MnPn]2 layers are also antiferromagnetically kOe), then subtracted from each other according to x < DM/DH; the coupled, leading to a G-type AF order and a magnetic unit cell twice resulting x(T) plots are shown in Figure 6b, c. Although there are low the size of the chemical unit cell. The NPD data at 4 K yield ordered temperature upturns below ,100 K, x(T), similar to BaMnAsF, moment values of 3.65(5) mB/Mn for BaMnAsF and 3.66(3) mB/Mn increase slowly with rising temperature. for BaMnSbF, which are lower than the value of 5.00 mB/Mn The long range antiferromagnetic order found from neutron dif- expected for the S 5 5/2 (high spin) Mn21 ions, assuming m 5 fraction results (see next section) at TN 5 338(1) K for BaMnAsF, gSmB with g 5 2. and TN 5 272(1) K for BaMnSbF do not manifest clearly in the Although lower than expected, the ordered moment values of magnetic susceptibility data (Figure 6). Magnetic susceptibility data 3.65(5) mB/Mn for BaMnAsF, and 3.66(3) mB/Mn for BaMnSbF sug- without a feature at TN is not unique to BaMnAsF and BaMnSbF; for gest local moment antiferromagnetism in these compounds. In 31 example, x(T) for LaMnPO (TN 5 375(5) K) is featureless up to 800 comparison, the ordered moment values are 0.2–1.0 mB/Fe in K; this was attributed to a very strong exchange coupling in the the delocalized spin-density-wave (SDW) antiferromagnets of 34 22 compound. Cases of increasing x(T) above TN have also been AEFe2As2 and LnFeAsO . Reduced moments and G-type ordering 32 26 3 33 35 reported for BaMn2As2 , BaMn2Bi2 , BaFe2As2 and LaFeAsO . have also been reported for BaMn2P2 (4.2(1) mB/Mn) and 34 BaMn2As2 (3.88(4) mB/Mn) . Among the quaternary ZrCuSiAs- type compounds of Mn, the ordered moments are 3.28(5) mB/Mn for LaMnPO (AF in the [MnP]2 layer and ferromagnetic, F, between 31 the layers) , 3.34(2) mB/Mn for LaMnAsO (intralayer AF and inter- 36 30 layer F) , and ,3 mB/Mn for PrMnSbO (AF C-type) . For these compounds, the reduced ordered moments have been attributed to a strong hybridization between pnictogen p and Mn d orbitals10,37. Figure 8b and 8c show temperature dependence of the (1 0 1/2) magnetic peak. AF ordering temperatures of TN (BaMnAsF) 5 338(1) K and TN (BaMnSbF) 5 272(1) K are obtained from a power 2 2b law fit I(T) / M (T) / (1-T/TN) of the order parameter, with b(BaMnAsF) 5 0.36(3) and b (BaMnSbF) 5 0.31(1), suggesting 3D Heisenberg class29. It is interesting that temperature dependence of the refined lattice parameters of BaMnAsF (Figure 7b) show a non- linear trend around room temperature; this may be indicative of a magnetoelastic coupling in BaMnAsF.

Figure 4 | For BaMnBiF, (a) Rietveld refinement (red line) of powder X- Electronic structure calculations. All three compounds are found to ray diffraction data (black dots), shown along with Bragg positions for be strongly magnetic with substantial Mn moments, in spite of the 1111 tetragonal I4/mmm phase (pink tick marks) and BaF2 impurity strong covalency between Mn and . We perform calcula- (turquoise tick marks). tions for both ferromagnetic (F) and in-plane nearest-neighbor

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Figure 5 | Temperature dependence of electrical resistivity, r(T), for polycrystalline pellets of (a) BaMnAsF and BaMnSbF, and (b) BaMnBiF. Insets illustrate lines (in red) corresponding to Arrhenius fit for the temperature region. antiferromagnetic (AF) spin configurations for the materials and insulators where DFT calculations give either no gaps or gaps much consider additional magnetic configurations for BaMnAsF. In all smaller than experiment. The inferred relative weakness of Mott- cases, the AF configuration was lower in energy than the F configu- Hubbard correlation effects in these materials is reminiscent of the ration. The energy differences between the two configurations are FeSCs, although it should be noted that this does not mean that the 0.48 eV/f.u for BaMnAsF, 0.37 eV/f.u for BaMnSbF, and 0.33 eV/f.u FeSCs are uncorrelated40,41. for BaMnBiF. These energies are extremely high and indicate high We find very strong covalency between the spin polarized Mn d magnetic ordering temperatures. For comparison, the prototypical orbitals and the pnictogen p orbitals in all three compounds. This is ferromagnet, bcc Fe (TC 5 1043 K), has a F – AF energy difference of seen in the electronic densities of states for the nearest neighbor ,0.4 eV in density functional calculations38. antiferromagnetic state (Figure 9). As may be seen from the projec- The qualitative reasons for these high energies may be seen in the tions the hybridization is strongly spin dependent, providing an electronic structures. The calculated densities of states for BaMnAsF explanation for the high energy scale associated with magnetic order. for the in-plane AF order are shown in Figure 9, with the corres- This is further seen by comparing the calculated electronic structures ponding band structures in Figure 10 (the plots for BaMnSbF and for the F and AF order. Figure 11 compares the Mn d projection of BaMnBiF are provided in Figures S5–S6). The and barium the spin resolved density of states (DOS) for BaMnAsF with these atoms are fully ionic, and the resulting ionic [BaF]1 layers form two orders. There is a strong reconstruction of the electronic struc- insulating barriers between the [MnPn]2 layers in the crystal struc- ture when going to the less favorable F order. In fact, this reconstruc- ture as is seen in the relatively weak dispersion of the occupied bands tion is so strong that the semiconducting gap is closed and because of along the c-axis (C-Z) in Figure 10. As may be seen, the band struc- this the magnetization is reduced from the nominal value of 5 mB/Mn tures with this magnetic order are semiconducting. The calculated to lower values of 4.0 mB, 4.3 mB and 4.4 mB for BaMnAsF, BaMnSbF gaps are 0.70 eV, 0.56 eV and 0.42 eV for BaMnAsF, BaMnSbF and and BaMnBiF, respectively (calculated based on the total spin mag- BaMnBiF, respectively. The values for BaMnAsF and BaMnSbF are netization in the cell, not the moments in LAPW spheres). As dis- close to those found from transport data, which is the expected cussed e.g. by Goodenough42, cases where the covalency and behavior of a material where the gap is between different transition electronic structure are strongly affected by magnetic order are cases metal d-manifolds and where Mott-Hubbard type Coulomb correla- where high exchange couplings can be expected. tions are not large39. This is in contrast to simple semiconductors In general local moment magnetism has two ingredients: (1) where DFT gaps are underestimates and especially Mott-Hubbard moment formation and (2) the interactions between the moments

Figure 6 | Temperature dependence of magnetic susceptibility, x(T), for (a) BaMnAsF, (b) BaMnSbF and (c) BaMnBiF. For BaMnAsF, inset shows a linear field-dependence of magnetization, M(H), at 5 K and 100 K. Note that (b) and (c) are derived using magnetization data under 20 kOe and 30 kOe assuming x < DM/DH, in order to eliminate ferromagnetic impurities (see text).

SCIENTIFIC REPORTS | 3 : 2154 | DOI: 10.1038/srep02154 5 www.nature.com/scientificreports

Figure 7 | (a) Rietveld plots of the neutron powder diffraction data for BaMnAsF collected at 4 K using 1.54 A˚ and 2.41 A˚ wavelengths. The two most prominent magnetic reflections, indexed as (1 0 1/2) and (1 0 3/2), are indicated by arrows. (b) Trends in lattice parameters for BaMnAsF as obtained from the NPD data. Dashed lines are intended as a guide to the eye. that to order. While divalent Mn can occur in different spin the SDW type ordering and the double stripe ordering are 0.12 eV states depending on the strength of the hybridization with , and 0.21 eV higher than the nearest neighbor AF order, respectively. here we find a near high spin case for all the magnetic orderings Therefore, in agreement with the NPD data, we conclude that the considered with similar spin moments in the Mn LAPW spheres nearest neighbor in-plane order is the probable ground state. for the F and AF cases (as well as the other cases for BaMnAsF). As mentioned, our calculations included spin orbit. In this case the However, the energy associated with moment formation is not so energy depends on the spin orientation through the magnetocrystal- much smaller than the ordering energy. For BaMnAsF in particular, line anisotropy. While this energy is small compared to the ordering non-spin-polarized calculations (no moments) yield an energy energy, it is relevant to the magnetic behavior. For BaMnAsF, we did 1.27 eV/f.u. higher than the nearest neighbor AF order, i.e. less than calculations with the moments oriented in the a-axis direction as well three times higher than the F order (0.48 eV/f.u.). along the c-axis direction. For the other cases discussed, the calcula- Consistent with this, we find very weak magnetic interactions in tions are done with the moments along the c-axis. With the experi- the c-axis direction. For BaMnAsF, we calculated the energy for mental the uniaxial c-axis direction is favored by doubled cells along c-axis for the F and in-plane AF cases with and 1.0 meV/f.u.. While this is a small energy, if correct, the result implies without alternation of spins along the c-axis. The energy differences that there will not be a strong Kosterlitz-Thouless type reduction in were below 1 meV per formula unit implying that this is a very highly the ordering temperature due to the near 2D character of the mater- two dimensional magnetic system. ial. To summarize, the calculations find that these materials are local In the case of BaMnAsF, we also considered other AF in-plane moment antiferromagnetic semiconductors with moderate band configurations. These were for the order observed in the Fe-pnictides gaps and strong spin-dependent hybridization between the Mn d consisting of chains of like spin Mn atoms (the so-called SDW order) states and the pnictogen p states. The materials are rather two dimen- and the double stripe pattern found in FeTe43 (see Ref. 43 for a sional both electronically and magnetically. The strong hybridiza- depiction of these orders). On a per formula unit basis, we find that tion to reconstructions of the band structure with changes in

Figure 8 | (a) The magnetic structure for BaMnAsF and BaMnSbF. Temperature dependence of (1 0 0.5) magnetic peak for (b) BaMnAsF and (c) BaMnSbF. Insets of (b) and (c) show evolution of (1 0 1/2) and (1 0 3/2) magnetic peaks with lowering temperature in low Q region.

SCIENTIFIC REPORTS | 3 : 2154 | DOI: 10.1038/srep02154 6 www.nature.com/scientificreports

Figure 9 | Electronic densities of states and projection for BaMnAsF in the nearest neighbor in plane antiferromagnetic state. The densities of states are per formula unit, both spins and the energy zero is at the valence band maximum. Figure 11 | Comparison of Mn-d projected electronic DOS for BaMnAsF, with nearest neighbor in-plane antiferromagnetic ordering (AF) and magnetic order. This in turn underlies very high magnetic energy ferromagnetic ordering (F). The energy zero is the valence band maximum for the AF case and the Fermi energy for the metallic F case. scales consistent with high TN that are confirmed in neutron diffraction. 32 26 3 temperatures are observed for BaMn2As2 , BaMn2Bi2 , BaFe2As2 33 Discussion and LaFeAsO . Such behavior may be indicative of strong exchange Three new 1111 fluoropnictides with the ZrCuSiAs-type structure, coupling among Mn moments in BaMnPnF. Another important namely BaMnAsF, BaMnSbF and BaMnBiF, are synthesized by feature of BaMnPnF phases is a strong hybridization between Mn reacting elements with BaF . The initial reactions of these compo- and Pn states, which is responsible for reduced ordered moment 2 m m nents give small plate crystallites that are suitable for structure refine- values of 3.65(5) B/Mn for BaMnAsF, and 3.66(3) B/Mn for ments using single crystal X-ray diffraction. Subsequent two-step BaMnSbF, as determined from the NPD data at 4 K. The observed 5 annealing procedure results in approximately single-phase products semiconducting antiferromagnetic behavior of BaMnPnF(Pn As, (,2% impurity content from PXRD and magnetization results). For Sb and Bi) is similar to the reported behavior in Mn-based oxypnic- tides LnMnPnO(Ln 5 La-Sm; Pn 5 P, As)11. BaMnPnF, the unit cell volumes and bond distances are much larger In conclusion, further studies of transition-metal-based ZrCuSiAs- compared to the isostructural Mn-based oxypnictides. type compounds in general, and BaMnPnF in particular, are war- Temperature dependence of electrical resistivity suggest that ranted. Although electronic structures of BaMnPnF are not similar to BaMnPnF are semiconductors with band gaps of E (BaMnAsF) 5 g that of the superconducting Fe-based 1111 compounds, recent 0.73 eV, E (BaMnSbF) 5 0.48 eV, and E (BaMnBiF) 5 0.003 eV. g g reports show that 1111 phases may demonstrate interesting variation These values are comparable to the theoretical gaps of 0.70 eV for of electrical and magnetic properties with doping and under applied BaMnAsF and 0.56 eV for BaMnSbF, but not 0.42 eV for BaMnBiF. pressure; for example, antiferromagnetic insulator LaMnAsO turns The large discrepancy in the band gap for BaMnBiF derived from the ferromagnetic metal when doped with hydrogen44. Another Mn- resistivity data is likely due to the influence of doping. Based on based compound, LaMnPO, transforms from an AF insulator to an electronic structure calculations, BaMnPnF are strongly magnetic AF correlated metal under pressure31. In addition, there is continued with a preferred G-type antiferromagnetic ground state. Neutron interest in 1111 phases due to the recent discovery of a high ther- powder diffraction (NPD) results give evidence for the G-type anti- moelectric efficiency in BiCuSeO, which is further enhanced by intro- 5 5 ferromagnetic order below TN 338(1) K for BaMnAsF, and TN duction of Cu defects27. 272(1) K for BaMnSbF. However, temperature dependence of mag- netization x(T) data on these polycrystalline pellets show no anom- Methods alies at TN, and x(T) increase with increasing temperature above TN. Synthesis. Dendritic Ba, Mn and As pieces, and Sb and Bi granules with purities Similar featureless x(T) data and non-Curie-Weiss behavior was greater than 99.9% are used as received from Alfa Aesar. Ultrapure BaF2 powder, from recently reported for LaMnPO31, and increasing x(T) above ordering Ventron Alfa Inorganics, is dried at 200uC for 3 h before using. Reactants in the stoichiometric ratio of Ba5BaF25Mn5Pn 5 1515252 are weighed inside a helium- filled glovebox and put into alumina crucibles. The alumina crucibles are then transferred into silica tubes and sealed under vacuum. The reaction mixtures are heated to 1000uC (30uCh21; dwell 6 h), then to 900uC (10uCh21; dwell 6 h), and subsequently to 300uC (30uCh21) after which the furnaces are switched off. This initial sintering step produced multi-phase reaction products, along with mm-size crystallites of 1111 phase in Pn 5 Sb and Bi, which are extracted for structural determinations using single crystal X-ray diffraction. The products are reground and pelletized inside the glovebox. The pellets are then placed inside alumina crucibles, enclosed in silica tubes, vacuum sealed, then annealed for a second time at 900uC (dwell 60 h). The third sintering step is the repeat of the latter annealing procedure. This only results in marginal improvement of phase purity as judged by slightly lower BaF2 impurity levels compared to the second sintering step.

Characterization. X-ray diffraction. For BaMnPnF(Pn 5 As, Sb, Bi), powder X-ray diffraction (PXRD) data are collected on a PANalytical X9Pert PRO MPD X-ray Diffractometer using monochromated Cu-Ka1 radiation. Scans are performed in 5– h Figure 10 | Band structure for BaMnAsF in the nearest neighbor in plane 65u (2 ) range, with a step size of 1/60u and 20–100 seconds/step counting time. Low temperature data collections are carried out using an Oxford Phenix closed cycle antiferromagnetic state. The energy zero is set to the valence band cryostat. Due to the air sensitivity of finely ground powders of Pn 5 Sb and Bi, the maximum. powders are loaded in a protective holder with a polycarbonate cover, inside the

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glovebox. Rietveld refinements are performed using GSAS45,46 software package. 7. Ren, Z.-A. et al. Superconductivity at 55 K in -Based F-doped Layered PXRD results are summarized in Figures 2 to 4, and Table S1 (see Supporting Quaternary Compounds Sm[O12xFx]FeAs. Chin. Phys. Lett. 25, 2215–2216 Information). (2008). For Pn 5 Sb and Bi, single crystal x-ray diffraction data are collected on a Bruker 8. Po¨ttgen, R. & Johrendt, D. Materials with ZrCuSiAs-type structure. Z. SMART APEX CCD-based diffractometer, which employs Mo Ka radiation (l 5 Naturforsch. 63b, 1135–1148 (2008). 0.71073 A˚ ). are selected under a microscope and cooled to 173(2) K under a 9. Yanagi, H. et al. Itinerant ferromagnetism in the layered crystals LaCoOX (X 5 P, cold stream. The data collection, data integration and refinement are carried As). Phys. Rev. B 77, 224431 (2008). out using the SHELXTL software package47. SADABS is used for semi-empirical 10. Xu, G., Ming, W., Yao, Y., Dai, X., Zhang, S.-C. & Fang, Z. Doping-dependent absorption correction based on equivalents. The structures are solved by direct phase diagram of LaOMAs (M 5 V-Cu) and electron-type superconductivity methods and refined by full matrix least-squares methods on F2. All sites are refined near ferromagnetic instability. Europhys. Lett. 82, 67002 (2008). with anisotropic atomic displacement parameters and full occupancies. Details of the 11. Muir, S. & Subramanian, M. A. ZrCuSiAs type layered oxypnictides: A bird’s eye crystallographic data and structure refinement parameters are given in Table 1. view of LnMPnO compositions. Progress in Solid State Chemistry 40, 41–56 Positional and equivalent isotropic displacement parameters, along with refined (2012). interatomic distances and angles are provided in Tables 2 and 3, respectively. Further 12. Watanabe, T. et al. -based oxyphosphide superconductor with a layered details of the crystal structure studies are summarized in the form of CIF crystal structure, LaNiOP. Inorg. Chem. 46, 7719–7721 (2007). (Crystallographic Information File) file (see Supporting Information). 13. Wu, G. et al. Superconductivity at 56 K in -doped SrFeAsF. J. Phys.: Condens. Matter 21, 142203 (2009). Elemental analysis. Energy-dispersive X-ray spectroscopy (EDS) measurements are 14. Cheng, P. et al. High-Tc superconductivity induced by doping rare-earth elements carried out using a Hitachi-TM3000 scanning electron microscope equipped with a into CaFeAsF. Europhys. Lett. 85, 67003 (2009). Bruker Quantax 70 EDS system. Data acquisition is carried out with an accelerating 15. Kabbour, H., Cario, L. & Boucher, F. Rational design of new inorganic compounds voltage of 15 kV in 2–3 min scanning time. EDS results confirm elemental compo- with the ZrSiCuAs structure type using 2D building blocks. J. Mater. Chem. 15, sitions of 1515151 for BaMnAsF, BaMnSbF and BaMnBiF. 3525–3531 (2005). 16. ICSDWeb, Version 2.1.1, FIZ Karlsruhe, 2011. Physical property measurements. For BaMnPnF(Pn 5 As, Sb, Bi), DC magnetization 17. Villars, P. & Cenzual, K. Pearson’s Crystal Data: Crystal Structure Database for measurements are carried out using a Quantum Design Magnetic Property Inorganic Compounds, ASM International, Materials Park, Ohio, 2008/9. Measurement System. Temperature dependence of magnetization experiments are 18. Saparov, B. & Bobev, S. Synthesis, crystal and electronic structures of the new performed on polycrystalline pellets under applied fields of 10 kOe, 20 kOe and 30 quaternary phases A5Cd2Sb5F(A 5 Sr, Ba, Eu), and Ba5Cd2Sb5Ox (0.5 , x , 0.7). kOe. Both zero field cooled (ZFC) and field cooled (FC) data are collected. Dalton Trans. 39, 11335–11343 (2010). Magnetization measurements as a function of field are carried out at 5 K, 100 K and 19. Kabbour, H., Cario, L., Jobic, S. & Corraze, B. P-type transparent conductors 300 K. Four-probe electrical resistivity measurements are carried out on a Quantum Sr12xNaxFCuS and SrF12xOxCuS: design, synthesis and physical properties. Design Physical Property Measurement System. J. Mater. Chem. 16, 4165–4169 (2006). 20. Motomitsu, E., Yanagi, H., Kamiya, T., Hirano, M. & Hosono, H. Synthesis, Thermal analysis. Thermogravimetric analysis (TGA) and differential thermal ana- structure and physical properties of layered semiconductors MCuFCh (M 5 Sr, lysis (DTA) on BaMnPnF(Pn 5 As, Sb) are performed using a Pyris Diamond TG/ Eu, Ch 5 S, Se). J. Solid State Chem. 179, 1668–1673 (2006). DTA from Perkin Elmer, under a stream of ultra-high purity argon . The mea- 21. Park, C.-H., Kykyneshi, R., Yokochi, A., Tate, J. & Keszler, D. A. Structure and surements are carried out on 20–25 mg pellet pieces in the temperature interval of physical properties of BaCuTeF. J. Solid State Chem. 180, 1672–1677 (2007). 323–1573 K (20 K min21). 22. Ganguli, A. K., Prakash, J. & Thakur, G. S. The iron-age of superconductivity: structural correlations and commonalities among the various families having – Neutron powder diffraction. Neutron powder diffraction experiments on BaMnPnF Fe-Pn- slabs (Pn 5 P, As and Sb). Chem. Soc. Rev. 42, 569–598 (2013). (Pn 5 As and Sb) are carried out using the HB-2A neutron powder diffractometer at 23. Ozawa, T. C. & Kauzlarich, S. M. Chemistry of layered d-metal pnictide and the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory (ORNL). their potential as candidates for new superconductors. Sci. Technol. Adv. Mater. 9, Measurements are performed using two different wavelengths of l 5 1.536 A˚ and 033003 (2008). 2.410 A˚ provided by the (115) and (113) reflections of a vertically focusing Ge 24. Brechtel, E., Cordier, G. & Schafer, H. New ternary alkaline earth compounds of monochromator; this allows for optimization of the instrument resolution function with . Z. Naturforsch. 33b, 820–822 (1978). for specific Q ranges. The data are collected by scanning the detector array consisting 25. Xia, S.-Q., Myers, C. & Bobev, S. Combined experimental and density functional of 443 He tubes in two segments to cover the total 2h range of 6–150u in steps of 0.05u; theory studies on the crystal structures and magnetic properties of overlapping detectors for the given step average the counting efficiency of each Mg(Mg12xMnx)2Sb2 (x < 0.25) and BaMn2Sb2. Eur. J. Inorg. Chem. 27, detector48. For the measurements, 4 g powder samples are confined inside 4262–4269 (2008). containers. For below room temperature measurements, samples are loaded inside a 26. Saparov, B. & Sefat, A. S. Crystals, magnetic and electronic properties of a new JANIS top-loading closed-cycle refrigerator, while for high temperatures experiments ThCr2Si2-type BaMn2Bi2 and K-doped compositions. J. Solid State Chem. (2013), up to 800uC, samples are loaded in an ILL vacuum furnace equipped with Nb heating submitted. elements. Rietveld refinements are performed using the FULLPROF program49. Spin 27. Liu, Y. et al. Remarkable enhancement in thermoelectric performance of BiCuSeO configurations compatible with the crystal symmetry are generated by group-theory by Cu deficiencies. J. Am. Chem. Soc. 133, 20112–20115 (2011). 50 analysis using the program SARAh .InPn 5 As compound, impurity phases of BaF2 28. Pauling, L. The Nature of the , Cornell University Press: Ithaca, NY, (1.5% weight fraction) and Mn2As (2.5%) are noted; in Pn 5 Sb compound, BaF2 1960. (2.5% weight fraction) and Mn12xO (2.4%) impurities are found. 29. Ashcroft, N. W. & Mermin, N. D. Solid State Physics, Thomson Learning Inc., USA, 1976. Electronic structure calculations. First principles calculations are performed using the 30. Kimber, S. A. J. et al. Local moments and symmetry breaking in metallic experimental crystal structure information data. The calculations are done within PrMnSbO. Phys. Rev. B 82, 100412 (2010). DFT using the generalized gradient approximation (GGA) of Perdew, Burke and 31. Simonson, J. W. et al. From antiferromagnetic insulator to correlated metal in Ernzerhof51 and the general potential linearized augmented planewave (LAPW) pressurized and doped LaMnPO. Proc. Nat. Acad. Sci. USA 109, E1815–E1819 method52 as implemented in the WIEN2k code53. Well-converged basis sets and (2012). Brillouin zone samplings are employed, along with LAPW sphere radii of 2.4 Bohr for 32. Johnston, D. C. et al. Magnetic exchange interactions in BaMn2As2: A case study 54 Ba, Mn, As, Sb and Bi, and 1.9 Bohr for F. Local orbitals are added to the basis to of the J1-J2-Jc Heisenberg model. Phys. Rev. B 84, 094445 (2011). include semi-core states and spin-orbit is included in the calculations. 33. McGuire, M. A. et al. Phase transitions in LaFeAsO: Structural, magnetic, elastic, and transport properties, heat capacity and Mo¨ssbauer spectra. Phys. Rev. B 78, 094517 (2008). 1. Kamihara, Y., Watanabe, T., Hirano, M. & Hosono, H. Iron-based layered 34. Singh, Y. et al. Magnetic order in BaMn2As2 from neutron diffraction superconductor La[O12xFx]FeAs (x 5 0.05–0.12) with Tc 5 26 K. J. Am. Chem. measurements. Phys. Rev. B 80, 100403 (2009). Soc. 130, 3296–3297 (2008). 35. Brock, S. L., Greedan, J. E. & Kauzlarich, S. M. Resistivity and magnetism of 2. Rotter, M., Tegel, M. & Johrendt, D. Superconductivity at 38 K in the iron AMn2P2 (A 5 Sr, Ba): The effect of structure type on physical properties. J. Solid (Ba12xKx)Fe2As2. Phys. Rev. Lett. 101, 107006 (2008). State Chem. 113, 303–311 (1994). 3. Sefat, A. S., Jin, R. Y., McGuire, M. A., Sales, B. C., Singh, D. J. & Mandrus, D. 36. Emery, N., Wildman, E. J., Skakle, J. M. S., Mclaughlin, A. C., Smith, R. I. & Fitch, Superconductivity at 22 K in Co-doped BaFe2As2 crystals. Phys. Rev. Lett. 101, A. N. Variable temperature study of the crystal and magnetic structures of the 117004 (2008). giant magnetoresistant materials LMnAsO (L 5 La, Nd). Phys. Rev. B 83, 144429 4. Wang, X. C. et al. The superconductivity at 18 K in LiFeAs system. Solid State (2011). Comm. 148, 538–540 (2008). 37. An, J., Sefat, A. S., Singh, D. J. & Du, M. H. Electronic structure and magnetism in 5. Hsu, F.-C. et al. Superconductivity in the PbO-type structure alpha-FeSe. Proc. BaMn2As2 and BaMn2Sb2. Phys. Rev. B 79, 075120 (2009). Nat. Acad. Sci. USA 105, 14262–14264 (2008). 38. Singh, D. J. Magnetism in bcc . Phys. Rev. B 45, 2258–2261 (1992). 6. Wang, C. et al. -doping-induced superconductivity up to 56 K in 39. Mattheiss, L. F. 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40. Qazilbash, M. M. et al. Electronic correlations in the iron pnictides. Nature Physics Acknowledgements 5, 647–650 (2009). This work was supported by the Department of Energy, Basic Energy Sciences, Materials 41. Vilmercati, P. et al. Direct probe of the variability of Coulomb correlation in iron Sciences and Engineering Division. Work at the High Flux Isotope Reactor, Oak Ridge pnictide superconductors. Phys. Rev. B 85, 235133 (2012). National Laboratory, was sponsored by the Scientific User Facilities Division, Office of Basic 42. Goodenough, J. B. Magnetism and the Chemical Bond, Wiley, New York, 1963. Energy Sciences, US Department of Energy. We thank R. Custelcean for his help with the 43. Singh, D. J. Superconductivity and magnetism in 11-structure iron single crystal X-ray diffraction measurements. in relation to the iron pnictides. Sci. Technol. Adv. Mater. 13, 054304 (2012). 44. Hanna, T., Matusishi, S., Kodama, K., Otomo, T., Shamoto, S. & Hosono, H. From antiferromagnetic insulator to ferromagnetic metal: Effects of Author contributions substitution in LaMnAsO. Phys. Rev. B 87, 020401 (2013). B.S. conceived the experiments, prepared the samples, carried out PXRD and SXRD 45. Larson, A. C. & Von Dreele, R. B. General Structure Analysis System (GSAS), Los experiments, electrical resistivity and magnetic susceptibility measurements, and wrote the Alamos National Laboratory Report LAUR 86–748,2000. paper. D.J.S. performed electronic structure calculations. V.O.G. carried out NPD 46. Toby, B. H. EXPGUI, a graphical user interface for GSAS. J. Appl. Crystallogr. 34, experiments. A.S.S. initiated the project, assisted with the magnetic susceptibility 210–213 (2001). measurements, supervised the experiments, analyzed the data and wrote the paper. All 47. ShelxTL 6.12, Bruker AXS, Inc., Madison, WI, 1997. authors reviewed the manuscript. 48. Garlea, V. O. et al. The high-resolution powder diffractometer at the high flux isotope reactor. Appl. Phys. A 99, 531–535 (2010). 49. Rodriguez-Carvajal, J. Recent advances in magnetic structure determination by Additional information neutron powder diffraction. Physica B 192, 55–69 (1993). Supplementary information accompanies this paper at http://www.nature.com/ 50. Wills, A. A new protocol for the determination of magnetic structures using scientificreports simulated annealing and representational analysis (SARAh). Physica B 276, 680–681 (2000). Competing financial interests: The authors declare no competing financial interests. 51. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation How to cite this article: Saparov, B., Singh, D.J., Garlea, V.O. & Sefat, A.S. Crystal, magnetic, made simple. Phys. Rev. Lett. 77, 3865–3868 (1996). and electronic structures, and properties of new BaMnPnF(Pn 5 As, Sb, Bi). Sci. Rep. 3, 52. Singh, D. J. & Nordstrom, L. Planewaves, Pseudopotentials and the LAPW Method, 2154; DOI:10.1038/srep02154 (2013). 2nd Edition, Springer, Berlin, 2006. 53. Blaha, P., Schwarz, K., Madsen, G., Kvasnicka, D. & Luitz, J. WIEN2k, An This work is licensed under a Creative Commons Attribution- Augmented Plane Wave 1 Local Oritals Program for Calculating Crystal NonCommercial-NoDerivs 3.0 Unported license. To view a copy of this license, Properties, K. Schwarz, Techn. Univ. Wien, Austria, 2001. visit http://creativecommons.org/licenses/by-nc-nd/3.0 54. Singh, D. Ground-state properties of -treatment of extended-core states. Phys. Rev. B 43, 6388–6392 (1991).

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SUBJECT AREAS: CORRIGENDUM: Crystal, magnetic, and electronic structures, and properties of MAGNETIC PROPERTIES new BaMnPnF(Pn 5 As, Sb, Bi) AND MATERIALS SUPERCONDUCTING Bayrammurad Saparov, David J. Singh, Vasile O. Garlea & Athena S. Sefat PROPERTIES AND MATERIALS The labels and title of the x-axis of Figure 9 are omitted in this Article. The correct Figure 9 appears below as SOLID-STATE CHEMISTRY Figure 1. ELECTRONIC PROPERTIES AND MATERIALS

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Published: 8 July 2013 Updated: 4 December 2013

Figure 1 |

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